JP2006216563A - Method of manufacturing organic electroluminescent element - Google Patents
Method of manufacturing organic electroluminescent element Download PDFInfo
- Publication number
- JP2006216563A JP2006216563A JP2006029027A JP2006029027A JP2006216563A JP 2006216563 A JP2006216563 A JP 2006216563A JP 2006029027 A JP2006029027 A JP 2006029027A JP 2006029027 A JP2006029027 A JP 2006029027A JP 2006216563 A JP2006216563 A JP 2006216563A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic
- organic layer
- manufacturing
- polymer film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 238000012546 transfer Methods 0.000 claims abstract description 83
- 239000010408 film Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000010409 thin film Substances 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims description 273
- 239000012044 organic layer Substances 0.000 claims description 122
- 229910052751 metal Inorganic materials 0.000 claims description 77
- 239000002184 metal Substances 0.000 claims description 77
- 229920006254 polymer film Polymers 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 37
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 31
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 31
- 230000005525 hole transport Effects 0.000 claims description 29
- -1 polydimethylsiloxane Polymers 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 14
- 230000005611 electricity Effects 0.000 claims description 13
- 238000000059 patterning Methods 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229920005549 butyl rubber Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 4
- 229920001230 polyarylate Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims 1
- 229920005570 flexible polymer Polymers 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 description 65
- 239000000463 material Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 15
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000007740 vapor deposition Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- HPGNGICCHXRMIP-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dithiine Chemical compound S1CCSC2=CSC=C21 HPGNGICCHXRMIP-UHFFFAOYSA-N 0.000 description 1
- 229910021076 Pd—Pd Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000813 microcontact printing Methods 0.000 description 1
- 238000001053 micromoulding Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/2457—Parallel ribs and/or grooves
Abstract
Description
本発明は、パターニングされた有機電界発光（Ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｔ：ＥＬ）素子の製造方法に係り、より具体的には、軟質の高分子フィルム層を含んだ薄膜転写用のドナーフィルムを利用して、光、熱、電気エネルギー及び圧力のうち、一つ以上によって上部ドナー層から下部アクセプタ層に有機層及び金属層を転写して、パターニングされた有機ＥＬ素子を製造する方法に関する。 The present invention relates to a method for manufacturing a patterned organic electroluminescence (EL) device, and more specifically, using a donor film for thin film transfer including a soft polymer film layer, The present invention relates to a method of manufacturing a patterned organic EL device by transferring an organic layer and a metal layer from an upper donor layer to a lower acceptor layer by one or more of heat, electric energy, and pressure.
有機ＥＬ素子は、蛍光または燐光有機層に電流を流し、電子と正孔とを有機層で結合させて光を発生させる現象を利用した自発光型素子であって、軽量であり、部品が簡単で、かつ製作工程が簡単であり、高画質及び光視野角の具現が可能である。また、動画を完璧に具現でき、高色純度の具現が可能であり、低消費電力、低電圧駆動で携帯用の電子機器に適した電気的な特性を有している。前記有機ＥＬ素子の用途は、ディスプレイまたはバックライトユニット等と非常に多様である。 An organic EL device is a self-luminous device that utilizes the phenomenon of generating light by passing an electric current through a fluorescent or phosphorescent organic layer and combining electrons and holes in the organic layer. In addition, the manufacturing process is simple, and high image quality and light viewing angle can be realized. In addition, the video can be realized perfectly, high color purity can be realized, and it has electrical characteristics suitable for portable electronic devices with low power consumption and low voltage drive. The use of the organic EL element is very diverse such as a display or a backlight unit.
一般的に、有機ＥＬ素子は、アノード、カソード、正孔輸送層（Ｈｏｌｅ Ｔｒａｎｓｐｏｒｔ Ｌａｙｅｒ：ＨＴＬ）、発光層（Ｅｍｉｔｔｉｎｇ Ｌａｙｅｒ：ＥＭＬ）及び電子輸送層（Ｅｌｅｃｔｒｏｎ Ｔｒａｎｓｐｏｒｔ Ｌａｙｅｒ：ＥＴＬ）を備える有機層からなる。また、正孔と電子とをさらに効率的に注入するために、アノードと正孔輸送層との間、そして、電子輸送層とカソードとの間にそれぞれ正孔注入層（Ｈｏｌｅ Ｉｎｊｅｃｔｉｏｎ Ｌａｙｅｒ：ＨＩＬ）と電子注入層（Ｅｌｃｔｒｏｎ Ｉｎｊｅｃｔｉｏｎ Ｌａｙｅｒ：ＥＩＬ）とをさらに備えても良い。 In general, an organic EL device includes an organic layer including an anode, a cathode, a hole transport layer (HTL), a light emitting layer (EML), and an electron transport layer (ETL). . Further, in order to inject holes and electrons more efficiently, a hole injection layer (HIL) is provided between the anode and the hole transport layer and between the electron transport layer and the cathode. And an electron injection layer (EIL).
この際、前記アノードから正孔注入層及び正孔輸送層を介して発光層に注入された正孔と、カソードから電子注入層及び電子輸送層を介して発光層に注入された電子がエキシトンを形成し、このエキシトンから正孔と電子との間のエネルギーに該当する光を発光させる。 At this time, the holes injected from the anode into the light emitting layer through the hole injection layer and the hole transport layer and the electrons injected from the cathode through the electron injection layer and the electron transport layer into the light emitting layer form excitons. The exciton emits light corresponding to the energy between holes and electrons.
前記アノードは、仕事関数の大きいＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）、ＩＺＯ（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ）、ＩＴＺＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｚｉｎｃ Ｏｘｉｄｅ）のような透明な導電性の物質から選択され、カソードは、仕事関数が小さく、化学的に安定した金属から選択される。 The anode is selected from transparent conductive materials such as ITO (Indium Tin Oxide), IZO (Indium Tin Oxide), and ITZO (Indium Tin Zinc Oxide) having a high work function, and the cathode has a low work function. Selected from chemically stable metals.
有機ＥＬ素子の一種として、パッシブマトリックス型の有機ＥＬ素子があるが、この素子を用い、複数層からなる有機膜が介在するアノードとカソードとの間に電流を流すと、二つの電極が交差する部分で発光する。この際、前記アノードは、有機ＥＬ層の上部に一定のパターンで形成される。 As a kind of organic EL element, there is a passive matrix type organic EL element, and when this element is used and a current is passed between an anode and a cathode in which an organic film composed of a plurality of layers is interposed, two electrodes cross each other. Lights at the part. At this time, the anode is formed in a predetermined pattern on the organic EL layer.
一方、有機ＥＬ素子のフルカラー化のためには、発光層、電子注入層、正孔注入層等の有機薄膜の微細パターンを形成することが必要である。 On the other hand, it is necessary to form a fine pattern of an organic thin film such as a light emitting layer, an electron injection layer, a hole injection layer, etc. in order to achieve full color of the organic EL element.
有機薄膜の微細パターンを形成する方法としては、有機薄膜上にフォトレジストをコーティング、露光及び現像して得られたフォトレジストパターンを利用することにより有機薄膜を微細加工するリソグラフィ法がある。しかし、この方法で形成された有機薄膜は、工程で使用される有機溶媒及び現像液の残留物などにより変形しうるため、実質的に適用するのがほとんど不可能である。さらに、他の方法としては、マスクを利用した真空蒸着法があるが、これは、数十ミクロン以下の微細加工が難しいという問題点がある。 As a method for forming a fine pattern of an organic thin film, there is a lithography method in which an organic thin film is finely processed by using a photoresist pattern obtained by coating, exposing and developing a photoresist on the organic thin film. However, since the organic thin film formed by this method can be deformed by the organic solvent used in the process and the residue of the developer, it is substantially impossible to apply. Furthermore, as another method, there is a vacuum vapor deposition method using a mask, but this has a problem that it is difficult to perform microfabrication of several tens of microns or less.
特許文献１は、フルカラー有機ＥＬ素子において高度にパターニングされた有機層を形成する方法を開示しているが、この方法は、蒸気蒸着の可能な有機ＥＬ物質を発熱装置を有する支持体上にコーティングした後、開口マスクを介して前記発光物質を、トランジスタアレイが備えられたＯＬＥＤ（Ｏｒｇａｎｉｃ Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）のボトム電極上に蒸気蒸着によって凹状の表面部に転写させる。この方法は、真空状態で有機物質を加熱して、蒸気状態でシャドーマスクを介して蒸着する熱蒸着に類似した方法である。 Patent Document 1 discloses a method of forming a highly patterned organic layer in a full-color organic EL element. In this method, an organic EL material capable of vapor deposition is coated on a support having a heating device. Thereafter, the light emitting material is transferred to the concave surface portion by vapor deposition on the bottom electrode of an OLED (Organic Light Emitting Diode) provided with a transistor array through an opening mask. This method is similar to thermal vapor deposition in which an organic substance is heated in a vacuum state and vapor deposition is performed through a shadow mask.
一方、レーザー転写法でパターニングする方法も知られている。レーザー転写法を使用してパターニングするためには、最小限の光源、転写フィルム及び基板が必要であり、光源から出る光が転写フィルムの光熱変換層により吸収されて熱エネルギーに変換され、この熱エネルギーにより転写フィルムの転写層を構成する物質が基板に転写されて、所望のイメージが形成される。 On the other hand, a patterning method using a laser transfer method is also known. Patterning using the laser transfer method requires a minimum light source, transfer film and substrate, and light emitted from the light source is absorbed by the light-to-heat conversion layer of the transfer film and converted to thermal energy. The material constituting the transfer layer of the transfer film is transferred to the substrate by energy, and a desired image is formed.
前記光熱変換層は、レーザーを介して入射された光を熱エネルギーに変えねばならないため、熱変換能力の大きい物質、例えば、カーボンブラック、ＩＲ−顔料などの有機化合物、アルミニウムなどの金属物質、前記金属物質の酸化物または前記の物質の混合物からなる。 Since the light-to-heat conversion layer must convert light incident through a laser into heat energy, a material having a large heat conversion capacity, for example, an organic compound such as carbon black or IR-pigment, a metal material such as aluminum, It consists of an oxide of a metallic material or a mixture of the aforementioned materials.
特許文献２には、基材フィルム、前記基材フィルムの上部に形成されている光熱変換層、及び前記光熱変換層の上部に形成されており、低分子物質からなる転写層を含み、前記転写層は、レーザーにより熱を伝達されて、レーザーが照射された転写層の一部は、光熱変換層との接着力の変化によって前記転写層が離脱され、レーザーにより照射されていない部分は、接着力により光熱変換層に固定されており、前記転写層に形成されている低分子物質が転写される有機ＥＬ素子の基板と前記低分子物質との接着力、及び前記光熱変換層と前記低分子物質との接着力が、前記転写層でレーザーを照射された領域の低分子物質と、レーザーを照射されていない領域の低分子物質との粘着力より大きいため、レーザーを照射された領域の低分子物質とレーザーを照射されていない領域の低分子物質とは、互いに分離されて前記光熱変換層から基板に物質転移が起こったことを特徴とする低分子フルカラー有機ＥＬ素子用のドナーフィルムを開示している。 Patent Document 2 includes a base film, a photothermal conversion layer formed on the base film, and a transfer layer formed on the photothermal conversion layer and made of a low molecular weight substance. The layer is transferred with heat by the laser, part of the transfer layer irradiated with the laser is detached from the transfer layer due to a change in adhesive force with the photothermal conversion layer, and the part not irradiated with the laser is bonded Adhesive force between the substrate of the organic EL element fixed to the light-to-heat conversion layer by force and onto which the low-molecular substance formed on the transfer layer is transferred and the low-molecular substance, and the light-to-heat conversion layer and the low molecule Since the adhesive strength with the substance is greater than the adhesive force between the low molecular weight material in the region irradiated with laser in the transfer layer and the low molecular weight material in the region not irradiated with laser, the low strength in the region irradiated with laser is low. Molecular material Disclosed is a donor film for a low-molecular full-color organic EL device that is separated from each other and has undergone mass transfer from the photothermal conversion layer to the substrate. .
しかし、前記レーザー転写方式でパターンを転写する場合、上部ドナーフィルムの可撓性が低下して、下部アクセプタフィルムとの接着力が低く、転写時に多くのエネルギーを必要とする。また、有機物の転写のみが可能であるため、例えば、パッシブマトリックス型の有機ＥＬ素子を製造する場合には、有機層パターニング後に金属を蒸着する工程を別途行わねばならないという煩雑さがある。さらに、光熱変換層を必ず必要とする。 However, when the pattern is transferred by the laser transfer method, the flexibility of the upper donor film is lowered, the adhesive force with the lower acceptor film is low, and a lot of energy is required at the time of transfer. In addition, since only an organic substance can be transferred, for example, when a passive matrix type organic EL element is manufactured, there is a trouble that a step of depositing a metal after an organic layer patterning must be performed separately. Furthermore, a photothermal conversion layer is always required.
また、非特許文献１に開示されているコールドウェルディング法は、２種類の異なる基板にコーティングされた金属膜の所望の部分を金属−金属接着力によりスタンピングした後に外す方法であって、基板上に積層された有機層に加えて、その上に全面蒸着されたカソード層上に金属がコーティングされたスタンプを大きな圧力で押圧した後に外すことにより、カソードのパターンを形成する。しかし、この際に大きな圧力を使用し、金属−金属接着力を利用するため、Ａｕ−Ａｕ、Ａｇ−Ａｇ、Ｐｄ−Ｐｄ等の仕事関数の大きい金属やそれらの他の金属との合金のみに限定され、転写する方式ではなく、リフト−オフ方式であるため、素子を完成させた後にパターニングする方法のみで使用可能である。 The cold welding method disclosed in Non-Patent Document 1 is a method of removing a desired portion of a metal film coated on two different substrates after stamping with a metal-metal adhesive force, In addition to the organic layer laminated on the cathode layer, a stamp coated with a metal on the cathode layer deposited on the entire surface of the organic layer is pressed with a large pressure and then removed to form a cathode pattern. However, since a large pressure is used at this time and a metal-metal adhesive force is used, only a metal having a large work function such as Au-Au, Ag-Ag, Pd-Pd or an alloy with these other metals is used. Since it is limited and is not a transfer method but a lift-off method, it can be used only by a patterning method after the element is completed.
一方、非特許文献２に掲載のカソード転写方法としては、ガラスモールドに分離促進層としてＳＡＭ層を形成し、その上にアルミニウム層を形成したものを、基板の上のアノード上に積層された有機層に大きな圧力で押圧してカソードを転写する方法もある。しかし、この場合にも、大きな圧力を使用してガラスモールドを使用するため、分離促進層を必ず必要とし、有機層に物理的な損傷を与えるおそれもある。 On the other hand, as a cathode transfer method described in Non-Patent Document 2, an organic layer in which a SAM layer is formed as a separation promoting layer on a glass mold and an aluminum layer is formed thereon is laminated on an anode on a substrate. There is also a method of transferring the cathode by pressing the layer with a large pressure. However, in this case as well, since a glass mold is used using a large pressure, a separation promoting layer is necessarily required, and there is a risk of physical damage to the organic layer.
一方、ポリジメチルシロキサン（ＰＤＭＳ）は、ガラス転移温度の低いシリコン系の弾性ゴムの一種であって、これをモールドとして利用したマイクロコンタクトプリンティング、マイクロモールディング及びナノトランスファプリンティング等の多様なパターニング方法が知られている。 On the other hand, polydimethylsiloxane (PDMS) is a kind of silicon-based elastic rubber having a low glass transition temperature, and various patterning methods such as microcontact printing, micromolding and nanotransfer printing using this as a mold are known. It has been.
特許文献３には、有機ＥＬ層が介在した第１電極と第２電極とが交差する部分を発光領域とするパッシブマトリックス型の有機ＥＬ素子において、基板上に第１方向に形成された第１電極と、前記第１電極を覆った基板の全面に形成された有機ＥＬ層と、前記有機ＥＬ層の上部に位置し、前記第１方向と交差する第２方向に位置し、Ｗ／Ｌ＝０．２〜２０及びＤ≧Ｌ×２０の関係式が成り立つ凹部と凸部とが互いに反復的に構成された凹凸部を有するＰＤＭＳモールドによる熱転写方式により外して、パターニングされた第２電極を形成するパッシブマトリックス型の有機ＥＬ素子が開示されている。前記方法では、モールドを第２電極に接着させた後に熱硬化させて、前記モールドの凸部と接着する第２電極を基板から外すことにより、パターニングされた第２電極を形成する。しかし、前記方法は、前記のコールドウェルディング法によって全面に蒸着された第２電極を相対的な結合力の差によって外すことを利用するという点で同じ方法である。
本発明が達成しようとする技術的課題は、ドナーフィルムの転写層と転写しようとするアクセプタフィルムとの接着力が良く、少ないエネルギーでも転写が可能であり、金属層だけでなく有機低分子及び高分子層のような複数の層を一度に転写でき、光熱変換層を必要としない薄膜転写用のドナーフィルムを利用して有機ＥＬ素子を製造する方法を提供するところにある。 The technical problem to be achieved by the present invention is that adhesion between the transfer layer of the donor film and the acceptor film to be transferred is good and transfer is possible with a small amount of energy. The present invention provides a method for producing an organic EL device by using a donor film for thin film transfer that can transfer a plurality of layers such as a molecular layer at a time and does not require a photothermal conversion layer.
前記技術的課題を達成するために、本発明の第１態様では、基板上にアノードを形成する工程と、前記アノード上に有機層を形成する工程と、前記有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された金属層を備える薄膜転写用のドナーフィルムの金属層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記有機層に前記金属層を転写させて、パターニングされたカソードを形成する工程と、を含む有機電界発光素子の製造方法が提供される。 In order to achieve the technical problem, in the first aspect of the present invention, a step of forming an anode on a substrate, a step of forming an organic layer on the anode, and patterning in an uneven shape on the organic layer One or more of heat, light, electricity and pressure after contacting the metal layer of the donor film for thin film transfer comprising the formed soft polymer film layer and the metal layer formed on the polymer film layer And transferring the metal layer to the organic layer to form a patterned cathode, and a method of manufacturing an organic electroluminescent device is provided.
本発明の第２態様では、基板上にアノードを形成する工程と、前記アノード上に第１有機層を形成する工程と、前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に前記第２有機層を転写させて、パターニングされた第２有機層を形成する工程と、前記パターニングされた第２有機層上に金属層を蒸着してカソードを形成する工程と、を含む有機電界発光素子の製造方法を提供する。 In the second aspect of the present invention, a step of forming an anode on a substrate, a step of forming a first organic layer on the anode, and a soft polymer patterned in a concavo-convex pattern on the first organic layer After contacting the second organic layer of the donor film for thin film transfer comprising the film layer and the second organic layer formed on the polymer film layer, one or more of heat, light, electricity and pressure are applied. Transferring the second organic layer to the first organic layer to form a patterned second organic layer; and depositing a metal layer on the patterned second organic layer to form a cathode. And a method for producing an organic electroluminescent device comprising the steps of:
本発明の第３態様では、基板上にアノードを形成する工程と、前記アノード上に第１有機層を形成する工程と、前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、前記高分子フィルム層に形成された金属層、及び前記金属層上に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に前記金属層及び第２有機層を転写させて、パターニングされた第２有機層及びカソードを形成する工程と、を含む有機電界発光素子の製造方法が提供される。 In the third aspect of the present invention, a step of forming an anode on a substrate, a step of forming a first organic layer on the anode, and a soft polymer patterned in a concavo-convex pattern on the first organic layer After contacting the second organic layer of the donor film for thin film transfer comprising the film layer, the metal layer formed on the polymer film layer, and the second organic layer formed on the metal layer, heat, light And applying at least one of electricity and pressure to transfer the metal layer and the second organic layer to the first organic layer to form a patterned second organic layer and cathode. A method for manufacturing a light emitting device is provided.
本発明の一具現例によれば、前記有機層、第１有機層及び第２有機層は、正孔輸送層、発光層及び電子輸送層を備え得る。 The organic layer, the first organic layer, and the second organic layer may include a hole transport layer, a light emitting layer, and an electron transport layer.
本発明の他の具現例によれば、前記軟質の高分子フィルム層は、ガラス転移温度が常温以下であり、ポリジメチルシロキサン（ＰＤＭＳ）等のシリコン系のゴムのようなシリコン系エラストマー、ポリブタジエン、ニトリルゴム、アクリルゴム、ブチルゴム、ポリイソプレン及びスチレン−ブタジエン共重合体などからなりうる。 According to another embodiment of the present invention, the soft polymer film layer has a glass transition temperature of room temperature or lower, a silicone elastomer such as a silicone rubber such as polydimethylsiloxane (PDMS), polybutadiene, Nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, styrene-butadiene copolymer and the like can be used.
本発明のさらに他の具現例によれば、前記軟質の高分子フィルム層は、パターニングされた側と反対側の面に支持層をさらに備え得る。 According to still another embodiment of the present invention, the soft polymer film layer may further include a support layer on a surface opposite to the patterned side.
本発明の第４態様では、前記方法で製造された有機ＥＬ素子が提供される。 In the 4th aspect of this invention, the organic EL element manufactured by the said method is provided.
本発明の有機ＥＬ素子の製造方法によれば、金属層と有機層とを一度に転写でき、低いエネルギーでも転写が可能であり、有機層の光化学反応を防止できるため、効率的にパターニングされた有機ＥＬ素子を製造できる。 According to the method for producing an organic EL element of the present invention, the metal layer and the organic layer can be transferred at a time, transfer is possible even with low energy, and the photochemical reaction of the organic layer can be prevented, so that the patterning is efficiently performed. An organic EL element can be manufactured.
本発明によって有機ＥＬ素子を製造すれば、金属層と有機物層とを一度に複数の層を転写でき、少ないエネルギーでも転写が可能であるため、容易で、かつ効率的にパターニングされた有機ＥＬ素子を製造できる。 If an organic EL device is manufactured according to the present invention, a plurality of layers can be transferred at once to a metal layer and an organic material layer, and transfer is possible with a small amount of energy. Therefore, the organic EL device can be easily and efficiently patterned. Can be manufactured.
以下、図面を参照して本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to the drawings.
本発明に係るパターニングされた有機ＥＬ素子の製造方法は、軟質の高分子フィルム層を含む薄膜転写用のドナーフィルムを使用するところにその特徴がある。前記高分子フィルム層は、厚さが０．５ｍｍ以上であることが好ましいが、０．５ｍｍ未満ではフィルムが柔軟過ぎて、加工が困難となる場合がある。また、前記高分子フィルムは、凹部と凸部とを有しており、凹部と凹部との間の距離に対する凸部と凸部との間の距離の比率は、好ましくは、０．１以上、さらに好ましくは、０．５以上である。０．１未満では、下部の有機層とのｍｐ接合時に上部の凹部の面が下部有機層と密着するサギング（ｓａｇｇｉｎｇ）現象が発生しうる。また、凸部の高さに対する広さの比率は、好ましくは、０．２以上、さらに好ましくは、１以上である。０．２未満では、凸部が圧力に耐えられずに崩れる現象が発生しうる。 The method for producing a patterned organic EL device according to the present invention is characterized in that a donor film for thin film transfer including a soft polymer film layer is used. The polymer film layer preferably has a thickness of 0.5 mm or more, but if it is less than 0.5 mm, the film may be too flexible and difficult to process. Further, the polymer film has a concave portion and a convex portion, and the ratio of the distance between the convex portion and the convex portion to the distance between the concave portion and the concave portion is preferably 0.1 or more, More preferably, it is 0.5 or more. If it is less than 0.1, a sagging phenomenon may occur where the surface of the upper concave portion is in close contact with the lower organic layer during mp junction with the lower organic layer. The ratio of the width to the height of the convex portion is preferably 0.2 or more, more preferably 1 or more. If it is less than 0.2, a phenomenon may occur in which the convex portion collapses without being able to withstand the pressure.
すなわち、基板上にアノードを形成した後、前記アノード上に形成される有機層の一部をパターニングするか、または前記有機層上に形成されるカソードをパターニングするか、または前記有機層の一部とカソードとを共にパターニングする場合に、薄膜転写用のドナーフィルムを利用して転写する。 That is, after forming an anode on a substrate, patterning a part of an organic layer formed on the anode, patterning a cathode formed on the organic layer, or part of the organic layer When both the cathode and the cathode are patterned, transfer is performed using a donor film for thin film transfer.
前記基板は、ガラスまたはプラスチックから製造されうる。 The substrate may be manufactured from glass or plastic.
この際、薄膜転写用のドナーフィルムは、ガラス転移温度が常温以下である凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された金属層、有機層または金属層及び有機層を備えるものであって、従来のレーザー転写法（Ｌａｓｅｒ Ｉｎｄｕｃｅｄ Ｔｈｅｒｍａｌ Ｉｍａｇｉｇ：ＬＩＴＩ）に使用されるドナーフィルムとは違って、光熱変換層が必要なく、低エネルギーでも転写が可能であるという利点がある。 At this time, the donor film for thin film transfer includes a soft polymer film layer patterned in an uneven shape having a glass transition temperature of room temperature or lower, and a metal layer, an organic layer, or a metal layer formed on the polymer film layer. Unlike the donor film used in the conventional laser induced thermal imaging (LITI), a photothermal conversion layer is not required and transfer is possible even at low energy. There are advantages.
ガラス転移温度が常温以下である軟質の高分子フィルム層は、転写しようとする層が付着される面が凹凸状にパターニングされたものである。このように凹部と凸部とが存在するように上部基板が備えられることにより、前記ドナーフィルムに光、熱などのエネルギーを加える際に、既存のレーザー転写法で行うようにスキャニングして加える必要がなく、全体的に光を一度に照射してもパターニングが可能であるという長所がある。したがって、単一工程で大量の転写が可能となる。 A soft polymer film layer having a glass transition temperature of room temperature or lower is obtained by patterning a surface on which a layer to be transferred is attached in an uneven shape. By providing the upper substrate so that there are concave and convex portions in this way, when applying energy such as light and heat to the donor film, it is necessary to scan and add as in the existing laser transfer method However, there is an advantage that patterning is possible even if light is irradiated at a time as a whole. Therefore, a large amount of transfer can be performed in a single process.
ガラス転移温度が常温以下である前記軟質の高分子フィルム層は、透明なシリコン系エラストマー、ポリブタジエン、ニトリルゴム、アクリルゴム、ブチルゴム、ポリイソプレン及びスチレン−ブタジエン共重合体からなる群から選択された１種以上であり、最も好ましくは、ポリジメチルシロキサンである。 The soft polymer film layer having a glass transition temperature of room temperature or lower is selected from the group consisting of a transparent silicone elastomer, polybutadiene, nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, and styrene-butadiene copolymer. More than species, most preferably polydimethylsiloxane.
また、前記高分子フィルム層を構成する高分子のガラス転移温度が常温以下であると、下部有機層と接触する時に共形の接触が可能であり、分子と原子との間で発生するファン・デル・ワールス引力が強く、熱または光などを多く加えなくても、高分子フィルム層と被転写層である有機層との接着力に優れており、転写が容易に行われうるため好ましい。 In addition, when the glass transition temperature of the polymer constituting the polymer film layer is normal temperature or lower, conformal contact is possible when contacting the lower organic layer, and a fan generated between molecules and atoms It is preferable because it has strong Dell attractive force, excellent adhesion between the polymer film layer and the organic layer as the transfer layer, and can be easily transferred without adding much heat or light.
まず、カソードのみを薄膜転写用のドナーフィルムを利用して転写して有機ＥＬ素子を製造する場合、基板上にアノードを形成する工程と、前記アノード上に有機層を形成する工程と、前記有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された金属層を備える薄膜転写用のドナーフィルムの金属層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記有機層に前記金属層を転写させて、パターニングされたカソードを形成する工程と、を含む方法で行われうる。なお、本形態において、金属層は高分子フィルム層の凸部のみならず凹部にも形成されていてもよい。 First, when manufacturing an organic EL device by transferring only a cathode using a donor film for thin film transfer, a step of forming an anode on a substrate, a step of forming an organic layer on the anode, and the organic After contacting a metal layer of a donor film for thin film transfer comprising a soft polymer film layer patterned in a concavo-convex shape and a metal layer formed on the polymer film layer on the layer, heat, light, And applying one or more of electricity and pressure to transfer the metal layer to the organic layer to form a patterned cathode. In this embodiment, the metal layer may be formed not only on the convex portion of the polymer film layer but also on the concave portion.
エネルギー源が光である場合、紫外線ランプで一度に全面露光できるため、非常に簡単な操作で大量の転写を行える。照射する光の照射時間は、ランプの強度によって調節されうる。例えば、強度が１０ｍＷ／ｃｍ２である場合、５〜１０分間処理できる。一度に短い時間に赤外線ランプで転写すべき場合には、選択的に光熱変換層を挿入してもよい。 When the energy source is light, since the entire surface can be exposed at once with an ultraviolet lamp, a large amount of transfer can be performed with a very simple operation. The irradiation time of the light to be irradiated can be adjusted by the intensity of the lamp. For example, when the intensity is 10 mW / cm 2 , the treatment can be performed for 5 to 10 minutes. If the transfer should be performed with an infrared lamp in a short time at a time, a photothermal conversion layer may be selectively inserted.
エネルギー源が熱である場合、６０ないし８０℃の温度で１０ないし３０分間処理すれば転写が可能である。 When the energy source is heat, transfer can be performed by processing at a temperature of 60 to 80 ° C. for 10 to 30 minutes.
エネルギー源が圧力である場合には、ドナーフィルム全体にわたって均一な圧力が加えられるようにパターニングされた軟質の高分子フィルム層のパターニングされた側と反対の側に支持層をさらに形成することが好ましい。前記支持層は、ガラス、ポリエチレンテレフタレート、ポリカーボネート、ポリエステル、ポリエチレンナフタレート、ポリエステルスルホネート、ポリスルホネート、ポリアリレート、フッ素化ポリイミド、フッ素化樹脂、ポリアクリル、ポリエポキシ、ポリエチレン、ポリスチレン、ポリアセテート及びポリイミドからなる群から選択された何れか一つでありうる。 When the energy source is pressure, it is preferable to further form a support layer on the side opposite to the patterned side of the soft polymer film layer that is patterned so that a uniform pressure is applied throughout the donor film. . The support layer is made of glass, polyethylene terephthalate, polycarbonate, polyester, polyethylene naphthalate, polyester sulfonate, polysulfonate, polyarylate, fluorinated polyimide, fluorinated resin, polyacryl, polyepoxy, polyethylene, polystyrene, polyacetate and polyimide. It may be any one selected from the group consisting of:
圧力は、１０ｋＰａないし１００ｍＰａの大きさで２ないし６０秒間加えうる。電気をエネルギー源として使用する場合に、印加される電流は、１ｍＡ／ｃｍ２ないし１０Ａ／ｃｍ２の大きさで１分ないし１時間流し得る。 The pressure may be applied at a magnitude of 10 kPa to 100 mPa for 2 to 60 seconds. When electricity is used as an energy source, the applied current can be applied at a magnitude of 1 mA / cm 2 to 10 A / cm 2 for 1 minute to 1 hour.
前記金属層は、２.０ｅＶないし６.０ｅＶの仕事関数を有する金属であって、第１金属層及び第２金属層の２層構造であってもよい。このような２層構造の場合、前記軟質の高分子フィルム層に付着される第１金属層は、仕事関数が大きく、前記高分子フィルム層と反応がよく起こらないものが良く、その例としては、Ａｌ、Ａｇ、Ａｕ、ＰｄまたはＰｔがある。前記第１金属層に付着される第２金属層は、仕事関数の小さい金属が好ましく、その例としては、Ｂａ、Ｃａ、Ｍｇ、ＣｓまたはＬｉ及びこれらの間または他の金属との合金がある。 The metal layer may be a metal having a work function of 2.0 eV to 6.0 eV, and may have a two-layer structure including a first metal layer and a second metal layer. In the case of such a two-layer structure, the first metal layer attached to the soft polymer film layer has a high work function and does not react well with the polymer film layer. , Al, Ag, Au, Pd or Pt. The second metal layer attached to the first metal layer is preferably a metal having a low work function, and examples thereof include Ba, Ca, Mg, Cs, Li, and alloys between these and other metals. .
転写しようとする層が金属層である場合、前記金属と軟質の高分子フィルム層との接着力より、前記金属とアクセプタフィルムをなす有機物との間の接着力が大きいため、エネルギーを少しだけ加えても、前記金属層が前記フィルム層から容易に分離されうる。 When the layer to be transferred is a metal layer, the adhesive force between the metal and the organic material forming the acceptor film is greater than the adhesive force between the metal and the soft polymer film layer, so a little energy is added. However, the metal layer can be easily separated from the film layer.
すなわち、ＰＤＭＳを軟質高分子フィルムとして使用したとした時、次の通りに接着力Ｗの差は、表面エネルギーγで表現できる。 That is, when PDMS is used as a soft polymer film, the difference in adhesive force W can be expressed by the surface energy γ as follows.
１が軟質高分子フィルムであり、２が金属であり、３が下部有機層であるとした場合には、最終式の右辺の第２項が第１項より非常に小さい。なぜなら、γ（金属）がγ（下部有機物）やγ（ＰＤＭＳ）より非常に大きいためである。したがって、下部有機層とＰＤＭＳとの表面エネルギーの差が接着力の差と等しくなる。ＰＤＭＳの場合は、表面エネルギーが１９．８ｍＪ／ｍ２と非常に低いため、下部有機層より弱い結合力を有する。下部有機物が、例えば発光物質であるＭＥＨ−ＰＰＶ［ポリ（２−メトキシ−５−（２’−エチル−ヘキシルオキシ）−１，４−フェニレンビニレン）］である場合には、２８．０ｍＪ／ｍ２と大きい表面エネルギーを示すため、外部エネルギーがなくても長い時間付けておけば、結合力の差によって転写が良好に行われ、外部エネルギー、すなわち、熱を８０℃で２０分以上加えれば、転写が行われる時間が速くなる。 When 1 is a soft polymer film, 2 is a metal, and 3 is a lower organic layer, the second term on the right side of the final formula is much smaller than the first term. This is because γ (metal) is much larger than γ (lower organic matter) and γ (PDMS). Therefore, the difference in surface energy between the lower organic layer and PDMS becomes equal to the difference in adhesion. In the case of PDMS, the surface energy is as low as 19.8 mJ / m 2, and thus has a weaker binding force than the lower organic layer. When the lower organic substance is, for example, MEH-PPV [poly (2-methoxy-5- (2′-ethyl-hexyloxy) -1,4-phenylenevinylene)] which is a light-emitting substance, 28.0 mJ / m 2 shows a large surface energy, so that if there is no external energy for a long time, the transfer is performed well due to the difference in binding force, and if external energy, that is, heat is applied at 80 ° C. for 20 minutes or more, The transfer time is faster.
ドナーフィルムによる転写が行われる被転写層である有機層は、正孔輸送層、発光層、電子輸送層を備え、必要に応じて電子注入層、正孔注入層、電子阻止層または正孔阻止層をさらに備え得る。 The organic layer, which is the transfer layer to be transferred by the donor film, includes a hole transport layer, a light emitting layer, and an electron transport layer, and an electron injection layer, a hole injection layer, an electron blocking layer, or a hole blocking layer as necessary. A layer may further be provided.
図１Ａ及び図１Ｂは、薄膜転写用のドナーフィルムを利用して金属層のみを転写して、パターニングされた有機ＥＬ素子を製造する方法を示す工程図である。これは、特にパッシブマトリックス型の有機ＥＬ素子を製造する際に有効な方法である。 1A and 1B are process diagrams showing a method of manufacturing a patterned organic EL element by transferring only a metal layer using a donor film for thin film transfer. This is an effective method particularly when a passive matrix type organic EL element is manufactured.
図１Ａの（ａ）工程では、パターニングされた軟質の高分子フィルム層１０１上に金属層１０２ａを蒸着して、薄膜転写用のドナーフィルムを作製する。次いで（ｂ）工程では、前記薄膜転写用のドナーフィルムの金属層１０２ａが、基板１０５、アノード１０４上に積層された有機層１０３上に接触するように位置させた後、熱、光、電気及び圧力のうち、１以上を加えて、ドナーフィルムを外せば、（ｃ）に示すように、金属層１０２ａが有機層１０３に転写されて有機ＥＬ素子が完成する。 In the step (a) of FIG. 1A, a metal layer 102a is deposited on the patterned soft polymer film layer 101 to produce a donor film for thin film transfer. Next, in the step (b), the metal layer 102a of the donor film for thin film transfer is positioned so as to be in contact with the organic layer 103 laminated on the substrate 105 and the anode 104, and then heat, light, electricity and If one or more of the pressures are applied to remove the donor film, the metal layer 102a is transferred to the organic layer 103 to complete the organic EL element, as shown in (c).
図１Ｂは、圧力を加えて転写を行う具現例を示す図面であって、圧力が薄膜転写用のドナーフィルムに均一に加えられるように、軟質の高分子フィルム層１０１のパターニングされた側と反対の側に支持層１００を形成することを除いては、図１Ａと同じ工程で行われる。 FIG. 1B is a view illustrating an embodiment in which a transfer is performed by applying pressure, and is opposite to the patterned side of the soft polymer film layer 101 so that the pressure is uniformly applied to the donor film for thin film transfer. Except for forming the support layer 100 on this side, the same process as in FIG. 1A is performed.
有機層のみを薄膜転写用のドナーフィルムを利用して転写して有機ＥＬ素子を製造する場合には、基板上にアノードを形成する工程と、前記アノード上に第１有機層を形成する工程と、前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に転写させてパターニングされた第２有機層を形成する工程と、前記パターニングされた第２有機層の凸面上に金属層を形成してカソードを形成する工程と、を含む方法で製造できる。 In the case of manufacturing an organic EL device by transferring only an organic layer using a donor film for thin film transfer, a step of forming an anode on a substrate, and a step of forming a first organic layer on the anode, A second organic layer of a donor film for thin film transfer comprising: a soft polymer film layer patterned in a concavo-convex pattern on the first organic layer; and a second organic layer formed on the polymer film layer. Forming the second organic layer patterned by applying one or more of heat, light, electricity and pressure to the first organic layer after the contact, and the second organic layer patterned And forming a cathode by forming a metal layer on the convex surface.
前記パターニングされた第２有機層を第１有機層に転写させた後、前記第２有機層上に金属層を蒸着させてカソードを形成できる。前記蒸着方法としては、熱蒸着法、電子ビーム蒸着法、スパッタリングがあり、この場合にも１層または２層の金属層を形成できる。 After the patterned second organic layer is transferred to the first organic layer, a metal layer is deposited on the second organic layer to form a cathode. Examples of the vapor deposition method include a thermal vapor deposition method, an electron beam vapor deposition method, and sputtering. In this case as well, one or two metal layers can be formed.
前記ドナーフィルムの第２有機層及び転写が起こる第１有機層は、電子輸送層、発光層、正孔輸送層を備えてもよく、必要に応じて電子注入層、正孔注入層、電子阻止層、正孔阻止層を備え得る。 The second organic layer of the donor film and the first organic layer where transfer occurs may include an electron transport layer, a light emitting layer, and a hole transport layer, and an electron injection layer, a hole injection layer, and an electron blocking layer as necessary. A layer, a hole blocking layer.
図２Ａ及び図２Ｂは、薄膜転写用のドナーフィルムを利用して有機層のみを転写してパターニングされた有機ＥＬ素子を製造する方法を示す工程図である。 2A and 2B are process diagrams showing a method of manufacturing a patterned organic EL element by transferring only an organic layer using a donor film for thin film transfer.
図２Ａの（ａ）工程では、パターニングされた軟質の高分子フィルム層２０１上に第２有機層２０２ｂを形成して薄膜転写用のドナーフィルムを作製する。次いで（ｂ）工程では、前記薄膜転写用のドナーフィルムの第２有機層２０２ｂが、基板２０５、アノード２０４上に積層された第１有機層２０３上に接触するように位置させた後、熱、光、電気及び圧力のうち、１以上を加えて、ドナーフィルムを外せば、（ｃ）に示すように第２有機層２０２ｂが第１有機層２０３に転写される。その後、（ｄ）工程で、パターニングされた第２有機層２０２ｂ上に金属層２０２ａを蒸着してカソードを形成することにより、有機ＥＬ素子が完成する。 In step (a) of FIG. 2A, a second organic layer 202b is formed on the patterned soft polymer film layer 201 to produce a thin film transfer donor film. Next, in step (b), the second organic layer 202b of the donor film for thin film transfer is positioned so as to contact the substrate 205 and the first organic layer 203 laminated on the anode 204, and then heat, When one or more of light, electricity, and pressure are applied to remove the donor film, the second organic layer 202b is transferred to the first organic layer 203 as shown in (c). Thereafter, in step (d), a metal layer 202a is deposited on the patterned second organic layer 202b to form a cathode, thereby completing an organic EL element.
図２Ｂは、圧力を加えて転写を行う具現例を示す図面であって、圧力が薄膜転写用のドナーフィルムに均一に加えられるように、軟質の高分子フィルム層２０１のパターニングされた側と反対の側に支持層２００を形成することを除いては、図２Ａと同じ工程で行われる。 FIG. 2B is a diagram illustrating an embodiment in which transfer is performed by applying pressure, and is opposite to the patterned side of the soft polymer film layer 201 so that the pressure is uniformly applied to the donor film for thin film transfer. Except for forming the support layer 200 on this side, the same process as in FIG. 2A is performed.
金属層と有機層とを共に薄膜転写用のドナーフィルムを利用して転写して有機ＥＬ素子を製造する場合、基板上にアノードを形成する工程と、前記アノード上に第１有機層を形成する工程と、前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された金属層、及び前記金属層上に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に前記金属層及び第２有機層を転写させて、パターニングされた第２有機層及びカソードを形成する工程と、を含む方法で製造できる。 When an organic EL device is manufactured by transferring both a metal layer and an organic layer using a donor film for thin film transfer, a step of forming an anode on the substrate and a first organic layer on the anode are formed. A soft polymer film layer patterned in a concavo-convex pattern on the first organic layer, a metal layer formed on the polymer film layer, and a second organic layer formed on the metal layer The metal layer and the second organic layer are transferred to the first organic layer by applying one or more of heat, light, electricity and pressure after contacting the second organic layer of the donor film for thin film transfer comprising And forming the patterned second organic layer and the cathode.
図３は、薄膜転写用のドナーフィルムを利用して金属層と第２有機層とを共に転写して、パターニングされた有機ＥＬ素子を製造する方法を示す工程図である。 FIG. 3 is a process diagram showing a method of manufacturing a patterned organic EL element by transferring a metal layer and a second organic layer together using a donor film for thin film transfer.
図３の（ａ）工程では、パターニングされた軟質の高分子フィルム層３０１上に第１金属層３０２ａ’、第２金属層３０２ａ”、及び第２有機層３０２ｂを順に形成して薄膜転写用のドナーフィルムを作製する。次いで（ｂ）工程では、前記薄膜転写用のドナーフィルムの第２有機層３０２ｂが基板３０５、アノード３０４上に積層された第１有機層３０３上に接触するように位置させた後、熱、光、電気及び圧力のうち、１以上を加えて、ドナーフィルムを外せば、（ｃ）に示すように金属層３０２ａと第２有機層３０２ｂとが第１有機層３０３に共に転写されて、パターニングされた有機ＥＬ素子が完成する。 In step (a) of FIG. 3, a first metal layer 302a ′, a second metal layer 302a ″, and a second organic layer 302b are sequentially formed on the patterned soft polymer film layer 301 to transfer a thin film. Next, in step (b), the second organic layer 302b of the donor film for thin film transfer is positioned so as to be in contact with the first organic layer 303 laminated on the substrate 305 and the anode 304. After that, if one or more of heat, light, electricity and pressure is applied and the donor film is removed, the metal layer 302a and the second organic layer 302b are attached to the first organic layer 303 as shown in FIG. The patterned organic EL element is completed by being transferred.
前記ドナーフィルムの第２有機層及び転写が起こる第１有機層は、電子輸送層、発光層、正孔輸送層を備えてもよく、必要に応じて電子注入層、正孔注入層、電子阻止層、正孔阻止層を備え得る。 The second organic layer of the donor film and the first organic layer where transfer occurs may include an electron transport layer, a light emitting layer, and a hole transport layer, and an electron injection layer, a hole injection layer, and an electron blocking layer as necessary. A layer, a hole blocking layer.
本発明の方法に使用される薄膜転写用のドナーフィルムは、軟質の高分子フィルム層、好ましくは常温以下のガラス転移温度を有する軟質の高分子フィルム層を製造する工程と、前記高分子フィルム層上に金属層、第２有機層または金属層及び第２有機層を形成させる工程と、を含む方法で製造できる。 The donor film for thin film transfer used in the method of the present invention comprises a step of producing a soft polymer film layer, preferably a soft polymer film layer having a glass transition temperature of room temperature or lower, and the polymer film layer. And a step of forming a metal layer, a second organic layer, or a metal layer and a second organic layer thereon.
前記軟質の高分子フィルム層が支持層をさらに備える場合、前記高分子フィルム層上に金属層、第２有機層または金属層と第２有機層とを蒸着させた後、高分子フィルム層の前記層が形成された側と反対の側に支持層を付着させうる。 When the soft polymer film layer further includes a support layer, after depositing a metal layer, a second organic layer or a metal layer and a second organic layer on the polymer film layer, the polymer film layer A support layer can be deposited on the side opposite the side on which the layer is formed.
前記パターニングされた軟質の高分子フィルム層は、次のような方法で製造できる。ウェーハ等からなるマスタを準備する。前記マスタは、所定の凹凸パターンを備えている。その後、軟質の高分子フィルム形成用の前駆体溶液を準備する。前記高分子フィルム形成用の前駆体溶液は、多様な化学メーカーから容易に購入であるが、例えば、ポリジメチルシロキサン（ＰＤＭＳ）を得ようとする場合、ダウケミカル社（Ｄｏｗ Ｃｈｅｍｉｃａｌ Ｉｎｃ．）のＳｙｌｇａｒｄ１８４シリーズを使用できる。準備された高分子フィルム形成用の溶液をマスタに注いだ後、前記溶液を適当な温度及び時間（例えば、ＰＤＭＳの場合、常温ないし１００℃で１時間ないし２４時間、好ましくは、６０℃ないし８０℃で１ないし３時間）で硬化させて、パターニングされた高分子フィルム層を形成する。そして、前記パターニングされた高分子フィルム層をマスタから外す。 The patterned soft polymer film layer can be manufactured by the following method. Prepare a master consisting of wafers. The master has a predetermined uneven pattern. Thereafter, a precursor solution for forming a soft polymer film is prepared. The precursor solution for forming the polymer film is easily purchased from various chemical manufacturers. For example, when obtaining polydimethylsiloxane (PDMS), Sylgard 184 of Dow Chemical Inc. Series can be used. After pouring the prepared polymer film-forming solution onto the master, the solution is heated to an appropriate temperature and time (for example, in the case of PDMS, from room temperature to 100 ° C. for 1 hour to 24 hours, preferably 60 ° C. to 80 ° C. Cured at 1 ° C. for 1 to 3 hours to form a patterned polymer film layer. Then, the patterned polymer film layer is removed from the master.
前記の通りに製造されたパターニングされた高分子フィルム層に、金属層または第２有機層を全面蒸着または塗布させる。この際、側面には蒸着されないように垂直蒸着法を利用するとよい。蒸着工程には、特別な制限がなく、スパッタリング法、電子ビーム蒸着法、熱蒸着法のような多様な蒸着法を使用できる。 A metal layer or a second organic layer is deposited on the entire surface of the patterned polymer film layer manufactured as described above. At this time, it is preferable to use a vertical vapor deposition method so that it is not vapor-deposited on the side surface. There are no particular restrictions on the deposition process, and various deposition methods such as sputtering, electron beam deposition, and thermal deposition can be used.
本発明に係る有機ＥＬ素子を構成するアノードは、ＩＴＯ、ＩＺＯ、ＩＴＺＯ、Ａｕ、Ａｇ、Ａｌ、ポリチオフェン、ポリピロール及びポリアニリン誘導体からなる群から選択された何れか一つでありうる。 The anode constituting the organic EL device according to the present invention may be any one selected from the group consisting of ITO, IZO, ITZO, Au, Ag, Al, polythiophene, polypyrrole, and polyaniline derivatives.
また、本発明に係る有機ＥＬ素子を構成するカソードは、２.０ｅＶないし６.０ｅＶの仕事関数を有する金属からなる１層または２層からなりうる。 In addition, the cathode constituting the organic EL device according to the present invention may be composed of one layer or two layers made of a metal having a work function of 2.0 eV to 6.0 eV.
本発明に係る有機ＥＬ素子を構成する有機層で正孔注入層は、ＰＥＤＯＴ（ｐｏｌｙ−３，４−ｅｔｈｙｌｅｎｅｄｉｏｘｙｔｈｉｏｐｈｅｎ）、ポリピロール、ポリアニリンのような伝導性の高分子であるか、またはＨＯＭＯ値が４．５〜６．０ｅＶである有機物でありうる。発光層としては、ポリフルオレン、スピロフルオレン、ポリフェニレン、ポリフェニレンビニレン、ポリチオフェン、ポリスルホン、ポリキノリン、ポリキノキサリン、ポリフェノキサジン、ポリチアジン及びその誘導体を含む高分子物質であるか、または分子量が１００００以下である低分子物質でありうる。正孔輸送層は、カルバゾール、アリールアミン系のような正孔輸送機能を有する基を含む有機低分子物質または高分子物質でありうる。電子輸送層は、キノリン、キノキサリン、金属錯体蛍光物質のような電子輸送機能を有する作用基を含む有機低分子物質または高分子物質でありうる。電子注入層は、ハロゲン化金属、酸化金属等からなりうる。 The hole injection layer in the organic layer constituting the organic EL device according to the present invention is a conductive polymer such as PEDOT (poly-3,4-ethylenedithiothiophene), polypyrrole, polyaniline, or has a HOMO value of 4. It may be an organic substance that is 5 to 6.0 eV. The light-emitting layer is a high molecular weight substance including polyfluorene, spirofluorene, polyphenylene, polyphenylene vinylene, polythiophene, polysulfone, polyquinoline, polyquinoxaline, polyphenoxazine, polythiazine and derivatives thereof, or a low molecular weight of 10,000 or less. It can be a molecular substance. The hole transport layer may be an organic low molecular weight material or a high molecular weight material including a group having a hole transport function such as carbazole or arylamine. The electron transport layer may be an organic low molecular weight material or a high molecular weight material including a functional group having an electron transport function such as quinoline, quinoxaline, and a metal complex fluorescent material. The electron injection layer can be made of a metal halide, a metal oxide, or the like.
以下、実施例を通じて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail through examples.
＜実施例１＞
＜薄膜転写用のドナーフィルムの製造（転写層が金属層のみである場合）＞
Ｓｙｌｇａｒｄ１８４Ａ及びＳｙｌｇａｒｄ１８４Ｂ（Ｄｏｗ Ｃｏｒｎｉｎｇ Ｉｎｃ．社製）を攪拌用の容器で１０：１の重量比で混合した。これから得たＰＤＭＳ形成用の溶液をあらかじめ準備したウェーハで作ったマスタ上に注いだ。前記マスタは、ストライプ状のパターンを備えたものである。マスタ上に注いだＰＤＭＳ形成用の溶液中の気泡を真空ポンプを利用して除去した後、オーブンに入れて６０℃ないし８０℃でＰＤＭＳ形成用の溶液を硬化させた後、マスタを除去して、ＰＤＭＳフィルム層を得た。
<Example 1>
<Manufacture of donor film for thin film transfer (when transfer layer is only metal layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS forming solution poured on the master using a vacuum pump, the PDMS forming solution is cured in an oven at 60 ° C. to 80 ° C., and then the master is removed. A PDMS film layer was obtained.
前記で得たＰＤＭＳフィルム層のパターニングされた面にＡｕを１×１０−７ｔｏｒｒ（１．３３×１０−５Ｐａ）の減圧下で電子ビーム蒸着して、２０ｎｍの厚さに蒸着させた。 Au was deposited on the patterned surface of the PDMS film layer obtained above by electron beam evaporation under a reduced pressure of 1 × 10 −7 torr (1.33 × 10 −5 Pa) to a thickness of 20 nm.
＜パターニングされた有機ＥＬ素子の製造＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００Å）ＩＴＯを５０ｍｍ×５０ｍｍ×０．７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして、１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した後、前記発光層の上部にアルミナキノン（Ａｌｑ３）からなる電子輸送層を３０ｎｍの厚さに蒸着した。前記で製造したドナーフィルムの凸部を接触させた後、ＩＲランプで１０分間照射して転写を行うことにより、パターニングされたカソードを形成して有機ＥＬ素子を完成した。
<Manufacture of patterned organic EL elements>
A glass substrate as a substrate and a first electrode and 15 Ω / cm 2 (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after UV and ozone cleaning for a minute. PFB (a hole transport material manufactured by Dow Chemical Co.) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. An electron transport layer made of aluminaquinone (Alq 3 ) is formed on the light emitting layer after forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer as a blue light emitting material on the hole transport layer. Was deposited to a thickness of 30 nm. After making the convex part of the donor film manufactured above contact, it was transferred by irradiating with an IR lamp for 10 minutes, thereby forming a patterned cathode to complete an organic EL device.
＜実施例２＞
＜薄膜転写用のドナーフィルムの製造（転写層が有機層のみである場合）＞
Ｓｙｌｇａｒｄ１８４Ａ及びＳｙｌｇａｒｄ１８４Ｂ（Ｄｏｗ Ｃｏｒｎｉｎｇ Ｉｎｃ．社製）を攪拌用の容器で１０：１の重量比で混合した。これから得たＰＤＭＳ形成用の溶液をあらかじめ準備したウェーハで作ったマスタ上に注いだ。前記マスタは、ストライプ状のパターンを備えたものである。マスタ上に注いだＰＤＭＳ形成用の溶液中の気泡を真空ポンプを利用して除去した後、オーブンに入れて６０℃ないし８０℃でＰＤＭＳ形成用の溶液を硬化させた後、マスタを除去して、ＰＤＭＳフィルム層を得た。
<Example 2>
<Manufacture of donor film for thin film transfer (when transfer layer is only organic layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS formation solution poured onto the master using a vacuum pump, the PDMS formation solution is cured at 60 ° C. to 80 ° C. in an oven, and then the master is removed. A PDMS film layer was obtained.
前記で得たＰＤＭＳフィルム層のパターニングされた面に電子輸送層をなす第２有機層としてＡｌｑ３を１×１０−７ｔｏｒｒ（１．３３×１０−５Ｐａ）の減圧下で３０ｎｍに蒸着させた。 Alq 3 was deposited at 30 nm under reduced pressure of 1 × 10 −7 torr (1.33 × 10 −5 Pa) as a second organic layer forming an electron transport layer on the patterned surface of the PDMS film layer obtained above. It was.
＜パターニングされた有機ＥＬ素子の製造＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００Å）ＩＴＯを５０ｍｍ×５０ｍｍ×０.７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして、１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した。前記で製造したドナーフィルムの凸部を接触させた後、ＩＲランプで１０分間照射して転写を行うことにより、パターニングされた電子輸送層を形成した。前記電子輸送層上に金属Ｃａ／Ａｌを５ｎｍ／２５０ｎｍの厚さに蒸着してカソードを形成することにより、有機ＥＬ素子を完成した。
<Manufacture of patterned organic EL elements>
A substrate and a glass substrate as a first electrode and 15 Ω / cm 2 (1200 mm) ITO were cut into a size of 50 mm × 50 mm × 0.7 mm, and cleaned with sonic alcohol and pure water for 5 minutes each, followed by 30 It was used after UV and ozone cleaning for a minute. A PFB (a hole transport material manufactured by Dow Chemical) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. A light emitting layer having a thickness of 70 nm was formed on the hole transport layer with a spirofluorene-based light emitting polymer that is a blue light emitting material. After making the convex part of the donor film manufactured above contact, it transferred by irradiating with an IR lamp for 10 minutes to form a patterned electron transport layer. An organic EL device was completed by depositing metal Ca / Al to a thickness of 5 nm / 250 nm on the electron transport layer to form a cathode.
＜実施例３＞
＜薄膜転写用のドナーフィルムの製造（転写層が金属層及び有機層である場合）＞
Ｓｙｌｇａｒｄ１８４Ａ及びＳｙｌｇａｒｄ１８４Ｂ（Ｄｏｗ Ｃｏｒｎｉｎｇ Ｉｎｃ．社製）を攪拌用の容器で１０：１の重量比で混合した。これから得たＰＤＭＳ形成用の溶液をあらかじめ準備したウェーハで作ったマスタ上に注いだ。前記マスタは、ストライプ状のパターンを備えたものである。マスタ上に注いだＰＤＭＳ形成用の溶液中の気泡を真空ポンプを利用して除去した後、オーブンに入れて６０℃ないし８０℃でＰＤＭＳ形成用の溶液を硬化させた後、マスタを除去して、ＰＤＭＳフィルム層を得た。
<Example 3>
<Manufacture of donor film for thin film transfer (when transfer layer is metal layer and organic layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS formation solution poured onto the master using a vacuum pump, the PDMS formation solution is cured at 60 ° C. to 80 ° C. in an oven, and then the master is removed. A PDMS film layer was obtained.
前記で得たＰＤＭＳフィルム層のパターニングされた面に電子ビーム蒸着法により金属Ａｕを２０ｎｍに蒸着させた。その後、Ｃａを熱蒸着により５ｎｍに蒸着し、蒸着された前記金属層上に電子輸送層となる第２有機層にＡｌｑ３を５ｎｍに蒸着させた。 On the patterned surface of the PDMS film layer obtained above, metal Au was evaporated to 20 nm by electron beam evaporation. Thereafter, Ca was vapor-deposited to 5 nm by thermal evaporation, and Alq 3 was vapor-deposited to 5 nm on the second organic layer serving as an electron transport layer on the vapor-deposited metal layer.
＜パターニングされた有機ＥＬ素子の製造１（光エネルギーを使用した場合）＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００Å）ＩＴＯを５０ｍｍ×５０ｍｍ×０．７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した後、前記で製造したドナーフィルムの凸部を接触させた後、ＩＲランプで１０分間照射して転写を行うことにより、パターニングされたカソード及び電子輸送層を形成して有機ＥＬ素子を完成した。
<Manufacture of patterned organic EL element 1 (when light energy is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm 2 (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer as a blue light emitting material on the hole transport layer, the convex portion of the donor film manufactured as described above is brought into contact with the IR lamp. The organic EL device was completed by forming a patterned cathode and an electron transport layer by transferring by irradiation for 10 minutes.
＜パターニングされた有機ＥＬ素子の製造２（電気エネルギーを使用した場合）＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００Å）ＩＴＯを５０ｍｍ×５０ｍｍ×０．７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして、１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した後、前記で製造したドナーフィルムの凸部を接触させた後、アノード及びカソードに接地を連結して３０分間１Ａ／ｃｍ２の電流を流して転写を行うことにより、パターニングされたカソード及び電子輸送層を形成して有機ＥＬ素子を完成した。
<Manufacture of patterned organic EL elements 2 (when electric energy is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm 2 (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A PFB (a hole transport material manufactured by Dow Chemical) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer, which is a blue light emitting material, on the hole transport layer, after contacting a convex portion of the donor film manufactured above, an anode and A ground was connected to the cathode, and a current of 1 A / cm 2 was applied for 30 minutes to perform transfer, whereby a patterned cathode and an electron transport layer were formed to complete an organic EL device.
＜パターニングされた有機ＥＬ素子の製造３（圧力を使用した場合）＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００Å）ＩＴＯを５０ｍｍ×５０ｍｍ×０．７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した後、前記で製造したドナーフィルムにガラス支持台を付着して凸部を下側に接触させた後、１５０ｋＰａの圧力を１５秒間加えて転写を行うことにより、パターニングされたカソード及び電子輸送層を形成して有機ＥＬ素子を完成した。
<Manufacture of patterned organic EL element 3 (when pressure is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm 2 (1200 mm) ITO were cut into a size of 50 mm × 50 mm × 0.7 mm, washed with ultrasonic waves in isopropyl alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer, which is a blue light emitting material, on the hole transport layer, a glass support is attached to the donor film manufactured as described above to form a convex portion. After making contact with the lower side, transfer was performed by applying a pressure of 150 kPa for 15 seconds to form a patterned cathode and an electron transport layer, thereby completing an organic EL device.
＜比較例１＞
＜パターニングされた有機ＥＬ素子の製造＞
基板及び第１電極としてガラス基板及び１５Ω／ｃｍ２（１２００℃）ＩＴＯを５０ｍｍ×５０ｍｍ×０．７ｍｍのサイズに切って、イソプロピルアルコール及び純水の中で各５分間超音波で洗浄した後、３０分間ＵＶ、オゾン洗浄して使用した。前記ＩＴＯ電極の上部にＰＦＢ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製の正孔輸送物質）をスピンコーティングして１０ｎｍの厚さの正孔輸送層を形成した。前記正孔輸送層の上部に青色発光物質であるスピロフルオレン系の発光高分子で７０ｎｍの厚さの発光層を形成した後、前記発光層の上部にＡｌｑ３からなる電子輸送層を３０ｎｍの厚さに蒸着した。１×１０−７ｔｏｒｒ（１．３３×１０−５Ｐａ）の減圧下で熱蒸着によって２０ｎｍのＡｕを蒸着して有機ＥＬ素子を完成した。
<Comparative Example 1>
<Manufacture of patterned organic EL elements>
After cutting a glass substrate and 15 Ω / cm 2 (1200 ° C.) ITO as a substrate and a first electrode into a size of 50 mm × 50 mm × 0.7 mm and washing with ultrasonic waves in isopropyl alcohol and pure water for 5 minutes each, It was used after being washed with UV and ozone for 30 minutes. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. A light emitting layer having a thickness of 70 nm is formed on the hole transporting layer with a spirofluorene-based light emitting polymer as a blue light emitting material, and then an electron transporting layer made of Alq 3 is formed on the light emitting layer with a thickness of 30 nm. Vapor deposited. An organic EL device was completed by depositing 20 nm of Au by thermal evaporation under reduced pressure of 1 × 10 −7 torr (1.33 × 10 −5 Pa).
＜評価試験１＞
本発明に係る方法で製造された有機ＥＬ素子の性能をテストするために、前記実施例１で製造した有機ＥＬ素子に対して電場の強度による電流及び発光強度を測定し、その結果を図４に示す。
<Evaluation test 1>
In order to test the performance of the organic EL device manufactured by the method according to the present invention, the current and emission intensity according to the electric field strength were measured for the organic EL device manufactured in Example 1, and the results are shown in FIG. Shown in
図４に示すように、本発明の製造方法で製造された有機ＥＬ素子は、ダイオードで表れる電流−電場の特性及び光強度−電場の特性を表すことにより、素子が良好に形成されたということが分かる。 As shown in FIG. 4, the organic EL device manufactured by the manufacturing method of the present invention was formed well by expressing the current-electric field characteristics and the light intensity-electric field characteristics expressed by the diodes. I understand.
＜評価試験２＞
本発明に係る方法で製造された有機ＥＬ素子の性能をテストするために、前記実施例１で製造した有機ＥＬ素子に対してＭｉｎｏｌｔａＣＳ１０００とＫｅｉｔｈｌｅｙ２３６とによって効率（輝度／電流）を測定し、さらに、比較例１で製造した有機ＥＬ素子についても同様に効率を測定した。測定の結果、実施例１によると０．０５ｃｄ／Ａの効率を示したのに対し、比較例１では効率が０．０１ｃｄ／Ａであったこれにより、本発明による素子製造方法がさらに優れているということが分かる。
<Evaluation Test 2>
In order to test the performance of the organic EL device manufactured by the method according to the present invention, the efficiency (luminance / current) was measured with the Minolta CS1000 and Keithley 236 for the organic EL device manufactured in Example 1, and The efficiency was measured in the same manner for the organic EL device produced in Comparative Example 1. As a result of measurement, the efficiency of 0.05 cd / A was shown in Example 1, whereas the efficiency in Comparative Example 1 was 0.01 cd / A, which further improved the device manufacturing method according to the present invention. You can see that
本発明は、有機電界発光に関連した技術分野に好適に適用され得る。 The present invention can be suitably applied to technical fields related to organic electroluminescence.
１０１、２０１、３０１ 軟質の高分子フィルム層、
１００、２００ 支持層、
１０２ａ、２０２ａ、３０２ａ 金属層、
１０３、１０３ａ 有機層、
２０３、３０３ 第１有機層、
２０２ｂ、３０２ｂ 第２有機層、
１０４、２０４、３０４ アノード、
１０５、２０５、３０５ 基板、
３０２ａ’ 第１金属層、
３０２ａ” 第２金属層。
101, 201, 301 soft polymer film layer,
100, 200 support layer,
102a, 202a, 302a metal layer,
103, 103a organic layer,
203, 303 first organic layer,
202b, 302b second organic layer,
104, 204, 304 anode,
105, 205, 305 substrate,
302a ′ first metal layer,
302a "second metal layer.
Claims (21)
前記アノード上に有機層を形成する工程と、
前記有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された金属層を備える薄膜転写用のドナーフィルムの金属層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記有機層に前記金属層を転写させて、パターニングされたカソードを形成する工程と、
を含む有機電界発光素子の製造方法。 Forming an anode on a substrate;
Forming an organic layer on the anode;
After contacting the metal layer of the donor film for thin film transfer comprising the soft polymer film layer patterned in an uneven shape on the organic layer, and the metal layer formed on the polymer film layer, heat, Applying one or more of light, electricity and pressure to transfer the metal layer to the organic layer to form a patterned cathode;
The manufacturing method of the organic electroluminescent element containing this.
前記アノード上に第１有機層を形成する工程と、
前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、及び前記高分子フィルム層に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に前記第２有機層を転写させて、パターニングされた第２有機層を形成する工程と、
前記パターニングされた第２有機層上に金属層を蒸着してカソードを形成する工程と、を含む有機電界発光素子の製造方法。 Forming an anode on a substrate;
Forming a first organic layer on the anode;
Contacting the second organic layer of a donor film for thin film transfer comprising a soft polymer film layer patterned in a concavo-convex pattern and a second organic layer formed on the polymer film layer on the first organic layer And then applying one or more of heat, light, electricity and pressure to transfer the second organic layer to the first organic layer to form a patterned second organic layer;
Depositing a metal layer on the patterned second organic layer to form a cathode, and a method for manufacturing an organic electroluminescent device.
前記アノード上に第１有機層を形成する工程と、
前記第１有機層上に、凹凸状にパターニングされた軟質の高分子フィルム層、前記高分子フィルム層に形成された金属層、及び前記金属層上に形成された第２有機層を備える薄膜転写用のドナーフィルムの第２有機層を接触させた後、熱、光、電気及び圧力のうち、１以上を加えて前記第１有機層に前記金属層及び第２有機層を転写させて、パターニングされた第２有機層及びカソードを形成する工程と、
を含む有機電界発光素子の製造方法。 Forming an anode on a substrate;
Forming a first organic layer on the anode;
Thin film transfer comprising a soft polymer film layer patterned in a concavo-convex pattern on the first organic layer, a metal layer formed on the polymer film layer, and a second organic layer formed on the metal layer After bringing the second organic layer of the donor film into contact, patterning is performed by transferring the metal layer and the second organic layer to the first organic layer by applying one or more of heat, light, electricity, and pressure. Forming the formed second organic layer and cathode;
A method for producing an organic electroluminescent device comprising
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050010616A KR20060089839A (en) | 2005-02-04 | 2005-02-04 | Methods for fabricating patterned organic electroluminescent devices |
| KR10-2005-0010616 | 2005-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006216563A true JP2006216563A (en) | 2006-08-17 |
| JP4904063B2 JP4904063B2 (en) | 2012-03-28 |
Family
ID=36913051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006029027A Active JP4904063B2 (en) | 2005-02-04 | 2006-02-06 | Method for manufacturing organic electroluminescent device |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7754520B2 (en) |
| JP (1) | JP4904063B2 (en) |
| KR (1) | KR20060089839A (en) |
| CN (1) | CN1838843A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008114353A1 (en) * | 2007-03-16 | 2008-09-25 | Pioneer Corporation | Thin film pattern forming method and organic device |
| JP2009016175A (en) * | 2007-07-04 | 2009-01-22 | Fujifilm Corp | Transfer material, forming method of pattern film, and manufacturing method of light-emitting element |
| JP2009037810A (en) * | 2007-07-31 | 2009-02-19 | Sumitomo Chemical Co Ltd | Organic electroluminescent element, and manufacturing method thereof |
| WO2009157077A1 (en) * | 2008-06-26 | 2009-12-30 | パイオニア株式会社 | Organic electroluminescent display panel and process for producing the same |
| JP2011198701A (en) * | 2010-03-23 | 2011-10-06 | Semiconductor Energy Lab Co Ltd | Film-deposition method and method for manufacturing light-emitting element |
| JP2012028318A (en) * | 2010-06-25 | 2012-02-09 | Semiconductor Energy Lab Co Ltd | Light-emitting element, light-emitting device, display, and electronic apparatus |
| JP2012079631A (en) * | 2010-10-05 | 2012-04-19 | Sony Corp | Organic el display device and method for manufacturing the same |
| KR20150063038A (en) | 2012-10-11 | 2015-06-08 | 소니 주식회사 | Organic el display device, manufacturing method therefor, ink and electronic apparatus |
| CN106926559A (en) * | 2017-03-24 | 2017-07-07 | 京东方科技集团股份有限公司 | Transfer substrate and preparation method thereof, OLED preparation method |
| WO2018052045A1 (en) * | 2016-09-16 | 2018-03-22 | 東京応化工業株式会社 | Substrate bonding method and laminated body production method |
| KR20180047399A (en) * | 2016-10-31 | 2018-05-10 | 울산과학기술원 | Method for manufacturing transparent electrode and electro substrate comprising transparent electrode |
| KR20180080561A (en) * | 2017-01-04 | 2018-07-12 | 한국과학기술원 | Flexible transparent electrode based on sonication assisted selective lift-off process and manufacturing method thereof |
| US10340473B2 (en) | 2015-02-24 | 2019-07-02 | Samsung Display Co., Ltd. | Organic light emitting display device with optical resonance structure and method of manufacturing the same |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7604916B2 (en) * | 2006-11-06 | 2009-10-20 | 3M Innovative Properties Company | Donor films with pattern-directing layers |
| US20090020910A1 (en) * | 2007-02-27 | 2009-01-22 | Stephen Forrest | System and method for depositing thin layers on non-planar substrates by stamping |
| US8101247B2 (en) * | 2007-06-19 | 2012-01-24 | The United States Of America As Represented By The Secretary Of The Navy | Sub-micron laser direct write |
| KR101434365B1 (en) * | 2008-01-22 | 2014-09-25 | 삼성디스플레이 주식회사 | fabrication method of organic light emitting device |
| KR100984182B1 (en) * | 2008-04-14 | 2010-09-28 | 삼성전자주식회사 | Non-volatile memory device, and method of fabricating the same |
| TWI524984B (en) * | 2008-10-09 | 2016-03-11 | 科學技術研究社 | Metal capped substrate imprints and method for forming the same |
| KR101121783B1 (en) * | 2010-01-22 | 2012-03-22 | 성균관대학교산학협력단 | Transfer sheet for transfer of metal electrode of organic light emitting diode and method of organic light emitting diode using the same |
| KR101149427B1 (en) * | 2010-05-27 | 2012-05-24 | 한국과학기술원 | Method for manufacturing organic electronic device |
| US9373666B2 (en) * | 2011-02-25 | 2016-06-21 | The Regents Of The University Of Michigan | System and method of forming semiconductor devices |
| KR101154838B1 (en) * | 2011-03-29 | 2012-06-18 | 한국과학기술원 | Method for manufacturing electronic device |
| KR20130081531A (en) | 2012-01-09 | 2013-07-17 | 삼성디스플레이 주식회사 | Donor film and method for manufacturing organic light emitting diode display using the same and organic light emitting diode display using the method |
| JP6110695B2 (en) | 2012-03-16 | 2017-04-05 | 株式会社半導体エネルギー研究所 | Light emitting device |
| EP2828901B1 (en) | 2012-03-21 | 2017-01-04 | Parker Hannifin Corporation | Roll-to-roll manufacturing processes for producing self-healing electroactive polymer devices |
| EP2837043B1 (en) | 2012-04-12 | 2017-11-22 | Parker-Hannifin Corporation | Eap transducers with improved performance |
| US9954159B2 (en) | 2012-08-16 | 2018-04-24 | Parker-Hannifin Corporation | Electrical interconnect terminals for rolled dielectric elastomer transducers |
| TW201436311A (en) * | 2012-10-16 | 2014-09-16 | 拜耳智慧財產有限公司 | Method of metallizing dielectric film |
| KR20140059376A (en) * | 2012-11-07 | 2014-05-16 | 삼성디스플레이 주식회사 | Apparatus for manufacturing organic layer and method for manufacturing organic light emitting display |
| KR102096243B1 (en) * | 2012-12-06 | 2020-05-27 | 엘지디스플레이 주식회사 | Pattern laminating film and method of fabricating organic electro-luminescent device using the same |
| KR20140129464A (en) * | 2013-04-29 | 2014-11-07 | 삼성디스플레이 주식회사 | Donor substrate, method of manufacturing a donor substrate and method of manufacturing an organic light emitting display device |
| KR101725947B1 (en) * | 2014-02-13 | 2017-04-11 | 주식회사 엘지화학 | method for manufacturing buried electrode by laser heat-transferring and buried electrode manufactured by the same |
| KR101595650B1 (en) * | 2014-04-04 | 2016-02-19 | 고려대학교 산학협력단 | Method of manufacturing a transparent substrate structure |
| KR101666790B1 (en) | 2015-01-22 | 2016-10-17 | 한국생산기술연구원 | Organic-inorganic composite light-emitting device possible to both mechanoluminescence and electroluminescence simultaneously and method for manufacturing thereof |
| KR102471349B1 (en) * | 2015-05-08 | 2022-11-29 | 고려대학교 산학협력단 | Method of manufacturing a pattern structure |
| CN104882569B (en) * | 2015-06-24 | 2017-01-25 | 京东方科技集团股份有限公司 | OLED display element, preparing method thereof, display panel and display device |
| CN107849687B (en) * | 2015-07-09 | 2020-01-14 | 奥博泰克有限公司 | Control of laser induced forward transfer spray angle |
| JP6642999B2 (en) | 2015-08-06 | 2020-02-12 | 株式会社ブイ・テクノロジー | Manufacturing method of organic EL device |
| KR101717471B1 (en) | 2015-10-19 | 2017-03-17 | 한국생산기술연구원 | Organic-inorganic composite korean paper light-emitting device and method for manufacturing thereof |
| TW201715769A (en) * | 2015-10-27 | 2017-05-01 | 謙華科技股份有限公司 | Method of fabricating organic light-emitting diode |
| KR101983330B1 (en) | 2015-10-30 | 2019-05-28 | 한국생산기술연구원 | Apparatus for Driving Light Emitting Device |
| CN106206427A (en) * | 2016-08-15 | 2016-12-07 | 京东方科技集团股份有限公司 | The manufacture method of display base plate, the manufacture method of display device and display base plate |
| KR101975289B1 (en) * | 2016-10-28 | 2019-05-07 | 주식회사 다원시스 | An manufacturing system for organic light emitting device and manufacturing method |
| KR101956283B1 (en) | 2016-12-01 | 2019-03-08 | 한국생산기술연구원 | Method for patterning organic thin film using laser beam and organic light emitting diode |
| CN106992268A (en) * | 2017-04-28 | 2017-07-28 | 京东方科技集团股份有限公司 | A kind of organic light emitting diode device and its manufacture method, display device |
| KR102423192B1 (en) * | 2017-09-06 | 2022-07-21 | 삼성디스플레이 주식회사 | Foldable display apparatus and the manufacturing method thereof |
| KR102106772B1 (en) | 2017-12-05 | 2020-05-06 | 한국생산기술연구원 | Method for patterning organic thin film using laser beam and organic light emitting diode |
| TW201943114A (en) * | 2018-03-31 | 2019-11-01 | 謙華科技股份有限公司 | Method for continuously fabricating organic light emitting diodes using thermal transfer film capable of improving conventional complicated vacuum evaporation process and increasing material utilization |
| CN112331792B (en) * | 2020-10-19 | 2021-12-10 | 浙江大学 | Light-emitting device based on polypyrrole conductive layer for flexible display screen |
| CN112701230B (en) * | 2020-12-23 | 2021-11-16 | 福州大学 | Method for preparing perovskite QLED electronic transmission layer by transferring ZnO nano film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07288185A (en) * | 1994-04-20 | 1995-10-31 | Dainippon Printing Co Ltd | Organic thin film electroluminescent (el) element |
| JP2002270368A (en) * | 2001-03-07 | 2002-09-20 | Sharp Corp | Transfer film and manufacturing method of organic electroluminescence element using it |
| JP2003133079A (en) * | 2001-10-26 | 2003-05-09 | Sharp Corp | Active matrix driving organic led panel and its manufacturing method |
| WO2004032575A1 (en) * | 2002-10-07 | 2004-04-15 | Koninklijke Philips Electronics N.V. | Method for manufacturing a light emitting display |
| WO2004061994A2 (en) * | 2002-12-20 | 2004-07-22 | The Trustees Of Princeton University | Methods of fabricating devices by low pressure cold welding |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5937272A (en) * | 1997-06-06 | 1999-08-10 | Eastman Kodak Company | Patterned organic layers in a full-color organic electroluminescent display array on a thin film transistor array substrate |
| KR100473589B1 (en) | 2002-03-12 | 2005-03-09 | 엘지.필립스 엘시디 주식회사 | Passive Matrix Type Organic Electroluminescent Device and Method for Fabricating the same |
| US20040191564A1 (en) * | 2002-12-17 | 2004-09-30 | Samsung Sdi Co., Ltd. | Donor film for low molecular weight full color organic electroluminescent device using laser induced thermal imaging method and method for fabricating low molecular weight full color organic electroluminescent device using the film |
-
2005
- 2005-02-04 KR KR1020050010616A patent/KR20060089839A/en not_active Application Discontinuation
-
2006
- 2006-01-27 CN CNA2006100045578A patent/CN1838843A/en active Pending
- 2006-02-06 US US11/347,659 patent/US7754520B2/en not_active Expired - Fee Related
- 2006-02-06 JP JP2006029027A patent/JP4904063B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07288185A (en) * | 1994-04-20 | 1995-10-31 | Dainippon Printing Co Ltd | Organic thin film electroluminescent (el) element |
| JP2002270368A (en) * | 2001-03-07 | 2002-09-20 | Sharp Corp | Transfer film and manufacturing method of organic electroluminescence element using it |
| JP2003133079A (en) * | 2001-10-26 | 2003-05-09 | Sharp Corp | Active matrix driving organic led panel and its manufacturing method |
| WO2004032575A1 (en) * | 2002-10-07 | 2004-04-15 | Koninklijke Philips Electronics N.V. | Method for manufacturing a light emitting display |
| WO2004061994A2 (en) * | 2002-12-20 | 2004-07-22 | The Trustees Of Princeton University | Methods of fabricating devices by low pressure cold welding |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008114353A1 (en) * | 2007-03-16 | 2008-09-25 | Pioneer Corporation | Thin film pattern forming method and organic device |
| JP2009016175A (en) * | 2007-07-04 | 2009-01-22 | Fujifilm Corp | Transfer material, forming method of pattern film, and manufacturing method of light-emitting element |
| JP2009037810A (en) * | 2007-07-31 | 2009-02-19 | Sumitomo Chemical Co Ltd | Organic electroluminescent element, and manufacturing method thereof |
| WO2009157077A1 (en) * | 2008-06-26 | 2009-12-30 | パイオニア株式会社 | Organic electroluminescent display panel and process for producing the same |
| JP2011198701A (en) * | 2010-03-23 | 2011-10-06 | Semiconductor Energy Lab Co Ltd | Film-deposition method and method for manufacturing light-emitting element |
| JP2012028318A (en) * | 2010-06-25 | 2012-02-09 | Semiconductor Energy Lab Co Ltd | Light-emitting element, light-emitting device, display, and electronic apparatus |
| JP2012079631A (en) * | 2010-10-05 | 2012-04-19 | Sony Corp | Organic el display device and method for manufacturing the same |
| US8883532B2 (en) | 2010-10-05 | 2014-11-11 | Sony Corporation | Organic EL display device and manufacturing method of the same |
| US9755149B2 (en) | 2012-10-11 | 2017-09-05 | Joled Inc. | Organic EL display unit, method of manufacturing the same, ink, and electronic apparatus |
| KR20150063038A (en) | 2012-10-11 | 2015-06-08 | 소니 주식회사 | Organic el display device, manufacturing method therefor, ink and electronic apparatus |
| US10340473B2 (en) | 2015-02-24 | 2019-07-02 | Samsung Display Co., Ltd. | Organic light emitting display device with optical resonance structure and method of manufacturing the same |
| US10847745B2 (en) | 2015-02-24 | 2020-11-24 | Samsung Display Co., Ltd. | Light emitting display device with conductive protection layers that are apart from each other |
| US11611055B2 (en) | 2015-02-24 | 2023-03-21 | Samsung Display Co., Ltd. | Organic light emitting display device with conductive protection layers that are spaced apart from each other and method of manufacturing the same |
| WO2018052045A1 (en) * | 2016-09-16 | 2018-03-22 | 東京応化工業株式会社 | Substrate bonding method and laminated body production method |
| US11491772B2 (en) | 2016-09-16 | 2022-11-08 | Tokyo Ohka Kogyo Co., Ltd. | Substrate bonding method and laminated body production method |
| KR20180047399A (en) * | 2016-10-31 | 2018-05-10 | 울산과학기술원 | Method for manufacturing transparent electrode and electro substrate comprising transparent electrode |
| KR101978886B1 (en) | 2016-10-31 | 2019-05-15 | 울산과학기술원 | Method for manufacturing transparent electrode and electro substrate comprising transparent electrode |
| KR20180080561A (en) * | 2017-01-04 | 2018-07-12 | 한국과학기술원 | Flexible transparent electrode based on sonication assisted selective lift-off process and manufacturing method thereof |
| CN106926559A (en) * | 2017-03-24 | 2017-07-07 | 京东方科技集团股份有限公司 | Transfer substrate and preparation method thereof, OLED preparation method |
| CN106926559B (en) * | 2017-03-24 | 2020-05-26 | 京东方科技集团股份有限公司 | Transfer printing substrate, manufacturing method thereof and manufacturing method of OLED device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4904063B2 (en) | 2012-03-28 |
| CN1838843A (en) | 2006-09-27 |
| US7754520B2 (en) | 2010-07-13 |
| US20060188697A1 (en) | 2006-08-24 |
| KR20060089839A (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4904063B2 (en) | Method for manufacturing organic electroluminescent device | |
| KR100611767B1 (en) | donor substrate for laser induced thermal imaging and method of fabricating electroluminescence display device using the same substrate | |
| US20060152147A1 (en) | Electroluminescent device and method for preparing the same | |
| TW200303152A (en) | Method and materials for transferring a material onto a plasma treated surface according to a pattern | |
| JP2008537631A (en) | Display manufacturing method | |
| JP2002343565A (en) | Manufacturing method of organic led display panel, organic led display panel manufactured by the same, and base film and substrate used for the same | |
| TWI342077B (en) | ||
| KR100623694B1 (en) | donor substrate for laser induced thermal imaging and method of fabricating electro-luminescence display device using the same substrate | |
| US20080309230A1 (en) | Full color organic electroluminescence display devices by thermal patterning using laser and method for manufacturing the same | |
| JP2006302865A (en) | Method of manufacturing organic electronic element | |
| Ashok Kumar et al. | Device engineering aspects of organic light-emitting diodes (OLEDs) | |
| TW200901531A (en) | Process for making contained layers | |
| JP2002280174A (en) | Donor film and organic led display panel manufactured by using it | |
| JP2009212079A (en) | Organic electroluminescent element, repairing device and its repairing method for organic electroluminescent element | |
| JP5072674B2 (en) | Organic electroluminescence device | |
| JP2003077653A (en) | Manufacturing method for electroluminescent element | |
| JP2003068455A (en) | Manufacturing method of organic el element | |
| JP2003168559A (en) | Organic led donor film and substrate, and organic led display panel using the same and its manufacturing method | |
| KR100796594B1 (en) | Donor substrate and method of fabricating thereof, and method of fabricating OLED using the same | |
| JP5002502B2 (en) | Method for manufacturing organic electroluminescence device | |
| JP2009129567A (en) | Method of manufacturing organic electroluminescent element and organic electroluminescent element | |
| JP4922977B2 (en) | Organic electroluminescence device | |
| US10026919B2 (en) | Organic light-emitting device | |
| KR100770273B1 (en) | Donor substrate and method of fabricating thereof | |
| KR20050052256A (en) | Method for manufacturing full colour organo electroluminescence display devices by thermal patterning using lazer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20081201 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090116 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101215 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101221 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110318 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110324 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110420 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110705 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111004 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111227 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120106 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4904063 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150113 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |